A series of Cu-ZnO-ZrO2 catalysts were prepared by sol-gel method using nitrate and citric acid as raw materials by adding ammonia water to adjust the pH value of the solution. XRD, thermal analysis (TG-DSC), N2 adsorption desorption (BET), H2 temperature programmed reduction (H2-TPR), CO2 temperature programmed desorption (CO2 -TPD), SEM,TEM and Fourier transform infrared (FTIR) spectroscopy were used to characterize the catalysts. The catalyst activity was evaluated in a high temperature and high pressure fixed bed reactor. The effect of pH of solution on the structure of dry gel and the performance of catalyst was discussed. The results showed that there was an uncoordinated free carboxylic acid in the dried gel prepared at pH 0.5, and some carboxylic acids were coordinated with metal ions through the carboxyl group. The free carboxylic acid was not present in the dried gel prepared at pH 4, 6, 8, and 10. The carboxylic acid was coordinated to the metal ion through the carboxyl group. The change of pH regulated the coordination ability between Cu2+, Zn2+, Zr4+ and citric acid. The catalyst prepared at pH 6 had a large specific surface area and copper dispersion, with a specific surface area of 92.5 m2/g and a copper dispersion of 18.63%, which exhibited better methanol synthesis by CO2 hydrogenation performance,Xco2=24.7%,SCH3OH=42.3%.